CN108249706A - A kind of silicon industry denitrogenation of waste water fluorine removal and the processing method of reuse - Google Patents
A kind of silicon industry denitrogenation of waste water fluorine removal and the processing method of reuse Download PDFInfo
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- CN108249706A CN108249706A CN201810151247.1A CN201810151247A CN108249706A CN 108249706 A CN108249706 A CN 108249706A CN 201810151247 A CN201810151247 A CN 201810151247A CN 108249706 A CN108249706 A CN 108249706A
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- Prior art keywords
- waste water
- fluorine
- pond
- fluorine removal
- water
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- 239000002351 wastewater Substances 0.000 title claims abstract description 166
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 127
- 239000011737 fluorine Substances 0.000 title claims abstract description 127
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 37
- 239000010703 silicon Substances 0.000 title claims abstract description 37
- 238000003672 processing method Methods 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000002253 acid Substances 0.000 claims abstract description 45
- 238000001556 precipitation Methods 0.000 claims abstract description 44
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000008676 import Effects 0.000 claims abstract description 20
- 239000006228 supernatant Substances 0.000 claims abstract description 20
- 230000001105 regulatory effect Effects 0.000 claims abstract description 17
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000012530 fluid Substances 0.000 claims abstract description 13
- 238000001764 infiltration Methods 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 8
- 241000894006 Bacteria Species 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 11
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 239000001110 calcium chloride Substances 0.000 claims description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 8
- 239000005416 organic matter Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- 238000009388 chemical precipitation Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 18
- 238000004065 wastewater treatment Methods 0.000 abstract description 7
- 230000002829 reductive effect Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 2
- 239000010842 industrial wastewater Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 24
- 239000012528 membrane Substances 0.000 description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 11
- 230000006872 improvement Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000001223 reverse osmosis Methods 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229960002050 hydrofluoric acid Drugs 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 239000010802 sludge Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012445 acidic reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 235000008216 herbs Nutrition 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000010812 mixed waste Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of silicon industry denitrogenation of waste water fluorine removal and the processing methods of reuse, belong to field of industrial waste water treatment, include the following steps：1) general waste water is imported into ultrafiltration+counter-infiltration system processing, is separated into fluorine-containing concentrated water containing nitrate nitrogen and clear water, (2) import level-one precipitation fluorine removal pond after the fluorine-containing concentrated water containing nitrate nitrogen is mixed with the high fluorine waste water of highly acid in regulating reservoir；3) control wastewater supernatant fluid pH value is no more than 1000mg/L in faintly acid and fluorinion concentration, and calcium fluoride precipitate is removed as body refuse, and supernatant imports denitrification pond；4) using denitrifying bacteria biochemical denitrification, by treated, waste water imports two-stage precipitation fluorine removal pond；(5) fluorine ion is made to form calcium fluoride precipitate and remove in two-stage precipitation fluorine removal pond, final outflow water meets discharge standard.Wastewater disposal basin floor space of the present invention is reduced；And the defects of fluorine removal need to largely add alkali and denitrification to need a large amount of acid addings in traditional handicraft is overcome, processing cost is reduced, conducive to popularization.
Description
Technical field
The invention belongs to technical field of waste water processing, are related to the processing method of a kind of fluorine-containing and nitrate nitrogen waste water, specifically
It is related to a kind of silicon industry denitrogenation of waste water fluorine removal and the processing method of reuse.
Background technology
In recent years, the silicon industry development such as China's photovoltaic, integrated circuit is rapid, and the same of great economic benefit is brought to society
When also bring new environmental problem.In polysilicon chip production process, making herbs into wool, erosion are generally carried out using nitric acid and hydrofluoric acid
It carves, is then cleaned using high purity water.Two class waste water can be generated in the process, and a kind of waste water is mixed by acid pickle and spent lye
It closes, because spent acid liquid measure is big, salkali waste liquid measure is small, so mixed waste water is acid strong, pH value is relatively low, fluoride ion and nitre state
Nitrogen is higher, referred to as strongly acid wastewater；For another kind of pH value of waste water close to neutrality, water is big, and fluoride ion amount is relatively low, referred to as general useless
Water.This two classes waste water, which all has to pass through fluorine removal, which denitrogenates processing, to discharge, otherwise can serious threat health and ecological environment.
In wastewater treatment, for water-saving consideration, it is desirable to which waste water to be as often as possible converted into clear water reuse again, at the same time it is wished that most
The waste water and waste residue discharged eventually is few as possible.
Content of fluoride ion height can inhibit the activity of denitrifying bacterium, be unfavorable for biochemical treatment, to containing high fluorine high-nitrate state nitrogen
The silicon industry such as photovoltaic, integrated circuit waste water is carried out in sub-prime collection and classification process, to remove F in advance-.Chemical precipitation method
Fluorine removal needs carry out under pH alkaline conditions, thus it is general using first alkali being added to adjust pH value to alkalinity, it is heavy then to add chemistry
Shallow lake agent fluorine removal, the alkali added in the process are excessive；But due to pH value raising in denitrification process, follow-up denitrogenation is also
Acid need to be added and carry out downward ph adjustment, such alkali and sour dosage are bigger, and excess base causes to waste with acid neutralization again.
Chinese invention patent, publication number：CN105152489A, publication date：It discloses a kind of fluorine-containing on December 16th, 2015
The processing method of the waste water of ion and nitrate ion.Specifically, this method comprises the following steps：1) adjusting control parameter；
2) denitrification denitrogenation；3) mud-water separation；4) fluorine removal is precipitated；5) flocculation sediment；It is adjusted with 6) effluent recycling.With denitrogenation after first fluorine removal
Traditional handicraft compare, the processing method of the invention, which passes through, carries out influent quality (such as ion concentration and pH value control parameter)
It is pre-adjusted, the fluctuation for avoiding influent quality has an impact the denitrification ability of follow-up denitrification process, realizes elder generation
The completely new technique of fluorine removal after denitrogenation, the fluorine removal process in traditional handicraft that reduces need to largely add lye and denitrification process and need largely
The processing cost of acid solution is added, more adapts to large-scale industrialization application.Its shortcoming is：(1) this method will generally give up
Water and strong acid waste water directly mix, and water to be treated is big, and the consumption of the chemical reagent such as soda acid is also big；(2) it is applicable in the party
The big floor space of regulating reservoir scale of method is also larger, and then causes fixed investment excessively high, and operation cost is also excessively high；(3) this method
In fail to realize waste water recycling to production unit；(4) in this method before denitrification denitrogenation, waste water does not control fluorine ion dense
Degree, when fluorinion concentration is more than that 1000mg/L will inhibit denitrification denitrogenation performance.
Chinese invention patent, publication number：CN106830554A, publication date：On June 13rd, 2017, disclose a kind of photovoltaic
The processing method of industrial wastewater.This method includes the following steps：By photovoltaic industry waste water be adjusted in regulating reservoir process with
It is homogenized water quality；By waste water by biochemical denitrification method being used to remove the nitrate nitrogen in waste water in anaerobic biological pond；Waste water is passed through
It, will be in the sludge part reuse to anaerobic biological pond that settled in sedimentation basin to remove the biological sludge in waste water in sedimentation basin；It will
Waste water is passed through the interior fluorine ion removed in a manner that coagulating sedimentation is detached and is combined using chemical reaction precipitation in waste water of reaction tank；
Waste water is passed through to remove the chemical sludge in waste water in clarifying basin, the partial sludge reuse got off will be deposited in clarifying basin to adjusting
It saves in pond.Invention retrieval except the dosage of fluorine material and the yield of chemical sludge, and the fluorine in treated waste water from
Sub- removal efficiency greatly improves, and can be stably held in 4~5ppm.Its shortcoming is：(1) this method by general waste water and
Strong acid waste water directly mixes, and water to be treated is big, and the consumption of the chemical reagent such as soda acid is also big；(2) it is applicable in this method
The big floor space of regulating reservoir scale is also larger, and then causes fixed investment excessively high, and operation cost is also excessively high；(3) in this method not
Waste water recycling can be realized to production unit；(4) in this method before denitrification denitrogenation, waste water does not control fluorinion concentration, when
Fluorinion concentration is more than that 1000mg/L will inhibit denitrification denitrogenation performance.
Therefore, based on prior art the defects of, need develop a kind of new processing method, so as to which silicon industry effectively be overcome to give up
Wastewater treatment capacity is big during water fluoridation is denitrogenated, needs to add in the problem of acid-base reagent is adjusted, soda acid dosage is big repeatedly.
Invention content
1. it to solve the problems, such as
For wastewater treatment capacity in existing silicon industry wastewater treatment process it is big, need to add in repeatedly acid-base reagent adjust and
The problem of soda acid dosage is big, the present invention provide a kind of new denitrogenation fluorine removal and the processing method of reuse.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows：
The present invention provides a kind of silicon industry denitrogenation of waste water fluorine removal and the processing systems of reuse, and the system is by general waste water
Pond, ultrafiltration+counter-infiltration system, reuse pool, spent acidic pond, regulating reservoir, level-one precipitation fluorine removal pond, denitrification pond, two level are sunk
Shallow lake fluorine removal pond and exhaust system composition, wherein general wastewater disposal basin, ultrafiltration+counter-infiltration system, regulating reservoir, level-one precipitation fluorine removal pond,
Denitrification pond, two-stage precipitation fluorine removal pond and exhaust system are sequentially connected, and the clear water water outlet of ultrafiltration+counter-infiltration system imports reuse
Pond is simultaneously back to the silicon industry production unit such as photovoltaic, integrated circuit, and waste water flows into from general wastewater disposal basin and from exhaust system stream
Go out, complete processing procedure.
As further improvement of the present invention, the processing system of a kind of silicon industry denitrogenation of waste water fluorine removal and reuse, including
Following steps：
(1) waste water in wastewater disposal basin general in silicon industry waste water is imported into ultrafiltration+counter-infiltration system processing, it will be described general
Production waste water is separated into fluorine-containing concentrated water containing nitrate nitrogen and clear water, and the clear water imports reuse pool, and fluorine-containing concentrated water containing nitrate nitrogen is led
Enter regulating reservoir；
(2) the fluorine-containing concentrated water containing nitrate nitrogen and the high fluorine waste water of highly acid from spent acidic pond are mixed in regulating reservoir
Level-one precipitation fluorine removal pond is imported after conjunction；
(3) sodium hydroxide, calcium hydroxide and calcium chloride are added in level-one precipitation fluorine removal pond, controls wastewater supernatant fluid pH value
It is no more than 1000mg/L in faintly acid and fluorinion concentration, calcium fluoride precipitate is removed as body refuse, and supernatant imports denitrification
Pond；
(4) organic matter is added into the denitrification pond as electron donor, using denitrifying bacteria biochemical denitrification, will be located
Waste water after reason imports two-stage precipitation fluorine removal pond；
(5) fluorine ion is made to form calcium fluoride precipitate using chemical precipitation method in two-stage precipitation fluorine removal pond and removed；Detection
F in the wastewater supernatant fluid discharged from two-stage precipitation fluorine removal pond-Concentration, nitrogen content and pH value, up to discharge standard after import discharge
System.
As further improvement of the present invention, fluorine-containing concentrated water containing nitrate nitrogen described in step (2) is given up with the high fluorine of highly acid
The mixed proportion of water is (2~1)：(1~2).
As further improvement of the present invention, the fluorine-containing volume of concentrated water containing nitrate nitrogen is 2%~5% in the step (1)；
Clear water volume is 95~98%.
As further improvement of the present invention, methanol, second are selected from as the organic matter of electron donor in step (4)
Any one or combination in alcohol, acetic acid, glucose.
As further improvement of the present invention, the chemical precipitation method in step (5) is input calcium hydroxide, chlorination successively
Calcium, PAC and PAM make fluorine ion form calcium fluoride precipitate.
As further improvement of the present invention, step (3) the control wastewater supernatant fluid pH value is 4~6.
Control denitrification pond goes out before two-stage precipitation fluorine removal pond is imported as further improvement of the present invention, in step (4)
The pH value of water is between 6.5~9, and total nitrogen concentration is within 30mg/L.
As further improvement of the present invention, the general waste water contains F-A concentration of 70~100mg/L, nitrate
For 100~200mg/L, pH is 5~7.
As further improvement of the present invention, the high fluorine waste water of highly acid contains F-A concentration of 5000~15000mg/L,
Nitrate is 1000~1600mg/L, and pH is 1~3.
3. advantageous effect
Compared with the prior art, beneficial effects of the present invention are：
(1) silicon industry denitrogenation of waste water fluorine removal of the invention and the processing method of reuse are collected, classification processing original based on sub-prime
Then, after a large amount of clear water in water is big, Funing tablet is low general waste water are detached first with ultrafiltration membrane and reverse osmosis membrane directly
Silicon industry production unit is returned, is greatly reduced and be will be fed into fluorine removal and denitrogenate the wastewater flow rate of unit, thus reduces wastewater disposal basin and accounts for
Ground area significantly reduces fixed investment cost；And the ingredient of general waste water does not contain the life for having inhibiting effect to UF membrane
Change metabolite and generate the calcium and magnesium ion that film dirt is blocked up, therefore high reusing rate can be obtained under the conditions of low operating cost.
(2) silicon industry denitrogenation of waste water fluorine removal of the invention and the processing method of reuse, it is different according to two kinds of waste water types, make
With ultrafiltration+counter-infiltration system first by water is big, the relatively low general waste water containing nitrate nitrogen and fluorinion concentration is located in advance
Highly concentrated fluorine-containing concentrated water containing nitrate nitrogen is obtained after reason, then is mixed, and add proper amount of hydrogen with the high fluorine waste water of highly acid
Sodium oxide molybdena and the mode of calcium hydroxide processing not only reduce wastewater treatment volume, while avoid the throwing of a large amount of acid-base reagents
Add；The fluoride ion directly generated in the silicon industry waste water such as photovoltaic, integrated circuit is utilized in this method simultaneously and nitrate nitrogen is higher
Waste water have the characteristics that in highly acid and follow-up denitrification process the characteristics of pH value increases, only to adopt in entire processing step
The mode for adding proper amount of sodium hydroxide and calcium hydroxide is taken to overcome and handles such waste water in the prior art using alkali acid
Reagent is adjusted repeatedly, causes the problem of alkali acid reagent dosage is larger, cost is higher, therefore the method for the present invention is conducive to promote.
(3) silicon industry denitrogenation of waste water fluorine removal of the invention and the processing method of reuse, will fluorine-containing concentrated water containing nitrate nitrogen and
After the high fluorine waste water of highly acid is simply mixed, proper amount of sodium hydroxide, calcium hydroxide, calcium chloride are added in, not only makes the wastewater pH be in
Faintly acid, and carrying out level-one fluorine removal precipitation can make fluorinion concentration then carry out next step biochemistry less than 1000mg/L and denitrogenate.Both
It ensure that fluorinion concentration is no more than 1000mg/L, and ensure denitrifying bacterium will not be inhibited active, and under solutions of weak acidity also
Be conducive to follow-up nitrifier activity；And under conditions of level-one fluorine removal precipitation, fluorine-containing concentrated water containing nitrate nitrogen is given up with the high fluorine of highly acid
Water need to only be simply mixed, and be not required to deliberately require ratio between the two, can further reduce waste water mixed volume.
(4) silicon industry denitrogenation of waste water fluorine removal of the invention and the processing method of reuse, meanwhile, by adding in suitable hydrogen-oxygen
Change calcium, calcium chloride progress level-one fluorine removal mode can control waste water fluorinion concentration to be no more than 1000mg/L, and in higher
1000mg/L can be such that fluorine ion is excessively deposited in solution after precipitating to avoid excess calcium hydroxide and calcium chloride is added in the prior art
Calcium ion to the inhibiting effect of denitrifying bacterium, remove extra calcium ion without carbonate such as other addition sodium carbonate,
Not only it had saved processing step but also had reduced the solid waste body refuse of discharge.
(5) silicon industry denitrogenation of waste water fluorine removal of the invention and the processing method of reuse, two-stage precipitation fluorine removal pond is set to
After denitrification pond, the consumption acid of anti-nitration reaction is made full use of to increase alkali effect, reducing waste water further reduces fluorine ion process
The dosage of middle alkali, neutralizes excess base without additionally acid is added, significantly reduces operation cost, more adapts to extensive
Industrial applications.
(6) silicon industry denitrogenation of waste water fluorine removal of the invention and the processing method of reuse, since the amount of reagent of input substantially subtracts
It is few, the body refuse amount of subsequent processing is needed also to be greatly decreased, body refuse cost of disposal is further reduced, is more suitable for large-scale industry
Change application.
Description of the drawings
Fig. 1 is the process route chart of the silicon industry denitrogenation of waste water fluorine removal of the present invention and the processing method of reuse.
Specific embodiment
The present invention is further described below with reference to specific embodiment.
Embodiment 1
A kind of place for being used to implement the silicon such as the photovoltaic, integrated circuit industry denitrogenation of waste water fluorine removal and the processing method of reuse
Reason system, including general wastewater disposal basin, ultrafiltration membrane, reverse osmosis membrane, reuse pool, spent acidic pond, regulating reservoir, level-one precipitation fluorine removal
Pond, denitrification pond, two-stage precipitation fluorine removal pond and exhaust system, general wastewater disposal basin, regulating reservoir, level-one precipitation fluorine removal pond, denitrification
Pond, two-stage precipitation fluorine removal pond and exhaust system are sequentially connected, and the spent acidic pond is connect with the regulating reservoir, reverse osmosis system
The clear water water outlet of system imports reuse pool and is simultaneously back to the silicon industry production unit such as photovoltaic, integrated circuit, and waste water is from general waste water
Pond flows into and is flowed out from exhaust system, completes a wheel processing procedure.
Certain corporate investment implements solar cell manufacturing project, and the waste water of discharge is mainly concentrated acid waste water, general waste water
Deng.Waste water treatment engineering design scale is 5000m3/ d, is divided into materializing strategy and biochemical treatment.Draining performs《Battery industry is dirty
Contaminate object discharge standard》(GB30484-2013) access city sewage plant processing after standard indirectly,
General waste water is essentially from each workshop section's pure water cleaning waste water, the regular draining of alkali spray column of acid mist, burned waste gas tail
Gas and ammonium hydroxide purge gas water spray tower handle regular draining, and feature is that water is big, and pH value is in neutrality slant acidity, fluorinion concentration
It is not high with the content of nitrate nitrogen, organic matter is there's almost no, therefore can be introduced directly into after active carbon filter filters super
Filter membrane and reverse osmosis membrane.As shown in Figure 1, general waste water be collected separately after through active carbon filter and cartridge filter, filter grain
Diameter is more than 5 μm of pollutant, successively into ultrafiltration, reverse osmosis membrane system.
Concentrated acid waste water is essentially from making herbs into wool process hydrochloric acid+hydrofluoric acid nitration mixture pickling waste waters, etching process nitric acid+sulfuric acid+hydrogen
It is fluoric acid pickling waste waters, hydrofluoric acid pickling waste waters, prerinse hydrochloric acid+hydrofluoric acid pickling waste waters, wet-chemical hydrofluoric acid pickling waste waters, wet
Chemical nitric acid cleans waste water, silicon chip is done over again, and pickling waste waters, graphite frame and quartz boat clean waste water.
As shown in Figure 1, a kind of silicon industry denitrogenation of waste water fluorine removal and the processing method of reuse, include the following steps：
(1) ultrafiltration+reverse osmosis system will be imported after the fluorine-containing general waste water filtering containing nitrate nitrogen collected in general wastewater disposal basin
System processing, wherein, the ultrafiltration membrane of ultrafiltration+counter-infiltration system selection is available from the DOW SFP-2880 of Dow Chemical, reverse osmosis
Permeable membrane is available from the BW30-400FR of Dow Chemical；The general waste water is separated into the fluorine-containing dense containing nitrate nitrogen of 2% volume
The clear water of water and 98% volume, the clear water import reuse pool, return to photovoltaic production unit, the fluorine-containing concentrated water containing nitrate nitrogen
Import regulating reservoir.
(2) the fluorine-containing concentrated water containing nitrate nitrogen and the high fluorine waste water of highly acid from spent acidic pond are mixed in regulating reservoir
Level-one precipitation fluorine removal pond is imported after conjunction；Fluorine-containing concentrated water containing nitrate nitrogen and the mixed proportion of the high fluorine waste water of highly acid are in the present embodiment
2：1, wherein, the fluorine-containing amount of concentrated water containing nitrate nitrogen and the high fluorine wastewater flow rate of highly acid are respectively 500m3/ d and 250m3/d。
(3) sodium hydroxide, calcium hydroxide and calcium chloride are added in level-one precipitation fluorine removal pond, so that pH value of waste water is in weak acid
Property, and Natural zeolite is tentatively removed, it is 4 to measure pH value, fluorinion concentration 800mg/L；Nitrate 1200mg/L；Calcirm-fluoride sinks
It forms sediment and is disposed as body refuse, supernatant imports denitrification pond.
(4) ethyl alcohol is added into the denitrification pond as electron donor, is converted into nitrate nitrogen using denitrifying bacteria
After nitrogen removes, the pH value of the denitrification pond water outlet is 6.5, and total nitrogen concentration 30mg/L, fluorinion concentration is constant, to generating
Biochemical sludge be disposed；The waste water in the denitrification pond is imported into two-stage precipitation fluorine removal pond again.
(5) calcium hydroxide, calcium chloride, PAC and PAM are put into successively in two-stage precipitation fluorine removal pond, fluorine ion is made to form fluorine
Change calcium precipitate to dispose as body refuse, detect the supernatant of waste water discharged from two-stage precipitation fluorine removal pond, F-A concentration of 3mg/
L, total nitrogen concentration be 30mg/L, pH value 9, by supernatant import exhaust system realize up to discharge.
The derived waste water F from level-one precipitation fluorine removal pond-Concentration is no more than 1000mg/L, and denitrification process will not be generated
It influences, and this pH value of waste water slant acidity, the pH value that the basicity that denitrification process generates can be discharged denitrification pond rises, institute
With without adding alkali again in regulating reservoir；The pond water outlet of level-one precipitation fluorine removal enters denitrification pond and carries out denitrification process, in denitrification
The ethyl alcohol of sufficient quantity is added in pond as denitrifying carbon source, the pH value of denitrification pond water outlet can reach 6.5~9, and total nitrogen concentration exists
Within 30mg/L, fluorinion concentration is constant；Supernatant enters two-stage precipitation fluorine removal pond after the water outlet of denitrification pond carries out mud-water separation,
It adds calcium oxide and calcium chloride forms calcium fluoride precipitate, in addition body refuse is disposed, obtained final outflow water water quality reaches emission request；
Overall quantity of alkali consumption is less than 0.7 kg/tonne of waste water, less than similar water process alkali consumption 40%.
Waste water quality, water and discharge standard are shown in Table 1 in the present embodiment.
1 waste water quality of table, water and discharge standard
It is computed, handles the energy consumption of such waste water and reagent cost is amounted to less than 6 yuan/ton, 20% is saved than traditional handicraft
Left and right.Floor space saves 15% or so compared with traditional handicraft.
Embodiment 2
As shown in Figure 1, system and process method step, with embodiment 1, difference is, general waste water separation in step (1)
For the fluorine-containing concentrated water containing nitrate nitrogen of 5% volume and the clear water of 95% volume；Fluorine-containing concentrated water containing nitrate nitrogen is with coming from acid in step (2)
Property wastewater disposal basin the high fluorine waste water of highly acid mixed proportion be 1.2：1.5；Fluorine ion in step (3) after level-one precipitation in waste water
A concentration of 880mg/L, nitrate 1500mg/L, wastewater supernatant fluid pH are 6；In step (4) organic matter be methanol, anti-nitre
Change the pH value of pond water outlet 8, total nitrogen concentration 25mg/L；The wastewater supernatant fluid discharged in two-stage precipitation fluorine removal pond in step (6)
Middle F-A concentration of 4mg/L, total nitrogen concentration 25mg/L, pH value 6；Overall quantity of alkali consumption is less than 0.8 kg/tonne of waste water, is less than
Similar water process alkali consumption 35%.
Waste water quality, water and discharge standard are shown in Table 2 in the present embodiment.
2 waste water quality of table, water and discharge standard
Embodiment 3
As shown in Figure 1, system and process method step, with embodiment 1, difference is, general waste water separation in step (1)
For the fluorine-containing concentrated water containing nitrate nitrogen of 3% volume and the clear water of 97% volume；Fluorine-containing concentrated water containing nitrate nitrogen is with coming from acid in step (2)
Property wastewater disposal basin the high fluorine waste water of highly acid mixed proportion be 1：2, wherein, the fluorine-containing amount of concentrated water containing nitrate nitrogen and concentrated acid waste water
Amount is respectively 300m3/ d and 600m3/d；Fluorinion concentration in step (3) after level-one precipitation in waste water is 950mg/L, nitrate nitrogen
A concentration of 1600mg/L, wastewater supernatant fluid pH are 5.5；Organic matter is acetic acid in step (4), and the pH value of denitrification pond water outlet is 9,
Total nitrogen concentration is 25mg/L；F in the wastewater supernatant fluid discharged in two-stage precipitation fluorine removal pond in step (6)-It is a concentration of 5mg/L, total
Nitrogen concentration is 25mg/L, pH value 6；Overall quantity of alkali consumption is less than 0.9 kg/tonne of waste water, less than similar water process alkali consumption
30%.
Waste water quality, water and discharge standard are shown in Table 3 in the present embodiment.
3 waste water quality of table, water and discharge standard
Embodiment 4
As shown in Figure 1, system and process method step, with embodiment 1, difference is, general waste water separation in step (1)
For the fluorine-containing concentrated water containing nitrate nitrogen of 4% volume and the clear water of 96% volume；Fluorine-containing concentrated water containing nitrate nitrogen is with coming from acid in step (2)
Property wastewater disposal basin the high fluorine waste water of highly acid mixed proportion be 2：1；Fluorinion concentration in step (3) after level-one precipitation in waste water
For 1000mg/L, wastewater supernatant fluid pH is 5；Organic matter is glucose in step (4), and the pH value of denitrification pond water outlet is 8.5, always
Nitrogen concentration is 15mg/L；F in the wastewater supernatant fluid discharged in two-stage precipitation fluorine removal pond in step (6)-A concentration of 2mg/L, total nitrogen
A concentration of 15mg/L, pH value 7；Overall quantity of alkali consumption is less than 1 kg/tonne of waste water, less than similar water process alkali consumption 25%.
Waste water quality, water and discharge standard are shown in Table 4 in the present embodiment.
4 waste water quality of table, water and discharge standard
The reverse osmosis membrane used in the present invention includes but not limited to the BW30-400 and BW30- purchased from Dow Chemical
400FR；Purchased from the TM720D-400 and TML20D-400 that east is beautiful；AG8040F-400F purchased from GE；And purchased from Hydranautics
CPA3-400 and LFC3-400 etc..The ultrafiltration membrane used in the present invention includes but not limited to the DOW purchased from Dow Chemical
SFP-2880；ZW1500-600 purchased from GE；Purchased from the HFU2020 that east is beautiful；L40n purchased from virtuous magnificent (former Siemens)；Purchased from the rising sun
The UNA-620A of chemical conversion；AQUAFLEX 55 and AQUAFLEX HP purchased from Pentair Water；And the Targa100 purchased from Coriolis and
KOCH-V10072-35-PVMC etc..
Schematically the invention and embodiments thereof are described above, this describes no restricted, attached drawing
Shown in be also the invention one of embodiment, practical structure is not limited thereto.So if this field
Those of ordinary skill enlightened by it, in the case where not departing from this creation objective, without creatively designing and the technology
The similar frame mode of scheme and embodiment should all belong to the protection domain of this patent.
Claims (10)
1. a kind of silicon industry denitrogenation of waste water fluorine removal and the processing system of reuse, it is characterised in that：The system by general wastewater disposal basin,
Ultrafiltration+counter-infiltration system, reuse pool, spent acidic pond, regulating reservoir, level-one precipitation fluorine removal pond, denitrification pond, two-stage precipitation remove
Fluorine pond and exhaust system composition, wherein general wastewater disposal basin, ultrafiltration+counter-infiltration system, regulating reservoir, level-one precipitation fluorine removal pond, anti-nitre
Change pond, two-stage precipitation fluorine removal pond and exhaust system to be sequentially connected, the clear water water outlet of ultrafiltration+counter-infiltration system imports reuse pool
And the silicon industry production unit such as photovoltaic, integrated circuit is back to, waste water is flowed into from general wastewater disposal basin and is flowed out from exhaust system, complete
Into processing procedure.
2. a kind of silicon industry denitrogenation of waste water fluorine removal and the processing method of reuse, it is characterised in that：Include the following steps：
(1) waste water in wastewater disposal basin general in silicon industry waste water is imported into ultrafiltration+counter-infiltration system processing, by the general production
Waste water is separated into fluorine-containing concentrated water containing nitrate nitrogen and clear water, and the clear water imports reuse pool, and fluorine-containing concentrated water containing nitrate nitrogen, which imports, to be adjusted
Save pond；
(2) after the fluorine-containing concentrated water containing nitrate nitrogen is mixed with the high fluorine waste water of the highly acid from spent acidic pond in regulating reservoir
Import level-one precipitation fluorine removal pond；
(3) sodium hydroxide, calcium hydroxide and calcium chloride are added in level-one precipitation fluorine removal pond, control wastewater supernatant fluid pH value is in weak
Acid and fluorinion concentration is no more than 1000mg/L, and calcium fluoride precipitate is removed as body refuse, and supernatant imports denitrification pond；
(4) organic matter is added into the denitrification pond as electron donor, using denitrifying bacteria biochemical denitrification, after processing
Waste water import two-stage precipitation fluorine removal pond；
(5) fluorine ion is made to form calcium fluoride precipitate using chemical precipitation method in two-stage precipitation fluorine removal pond and removed；It detects from two
F in the wastewater supernatant fluid discharged in grade precipitation fluorine removal pond-Concentration, nitrogen content and pH value, up to discharge standard after import exhaust system.
3. according to silicon industry denitrogenation of waste water fluorine removal and the processing method of reuse described in claim 2, it is characterised in that：Step
(2) fluorine-containing concentrated water containing nitrate nitrogen described in and the mixed proportion of the high fluorine waste water of highly acid are (2~1)：(1~2).
4. according to silicon industry denitrogenation of waste water fluorine removal and the processing method of reuse described in Claims 2 or 3, it is characterised in that：
The fluorine-containing volume of concentrated water containing nitrate nitrogen is 2%~5% in the step (1)；Clear water volume is 95~98%.
5. according to silicon industry denitrogenation of waste water fluorine removal and the processing method of reuse described in claim 4, it is characterised in that：Step
(4) any one or combination in as the organic matter of electron donor in methanol, ethyl alcohol, acetic acid, glucose.
6. according to silicon industry denitrogenation of waste water fluorine removal and the processing method of reuse described in claim 2 or 5, it is characterised in that：
Chemical precipitation method in step (5) makes fluorine ion form calcirm-fluoride and sinks to put into calcium hydroxide, calcium chloride, PAC and PAM successively
It forms sediment.
7. according to silicon industry denitrogenation of waste water fluorine removal and the processing method of reuse described in Claims 2 or 3, it is characterised in that：
Step (3) the control wastewater supernatant fluid pH value is 4~6.
8. according to silicon industry denitrogenation of waste water fluorine removal and the processing method of reuse described in Claims 2 or 3, it is characterised in that：
Between 6.5~9, total nitrogen concentration exists the pH value of control denitrification pond water outlet before importing two-stage precipitation fluorine removal pond in step (4)
Within 30mg/L.
9. according to silicon industry denitrogenation of waste water fluorine removal and the processing method of reuse described in claim 7, it is characterised in that：It is described
General waste water contains F-A concentration of 70~100mg/L, nitrate are 100~200mg/L, and pH is 5~7.
10. according to silicon industry denitrogenation of waste water fluorine removal and the processing method of reuse described in claim 8, it is characterised in that：Institute
The high fluorine waste water of highly acid is stated containing F-A concentration of 5000~15000mg/L, nitrate are 1000~1600mg/L, pH for 1~
3。
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| CN115849589A (en) * | 2022-01-26 | 2023-03-28 | 浙江工业大学 | Fluoride ion in photovoltaic industry waste water is inhaled coherent electrochemical denitrification cooperative treatment method |
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